Manufacture of aromatic stibinic acid.



"trichlorid; and byjthe action of this sub cum mm m muss scnmm'n'or nannnnun, mama nnnsnnn', one a i To all w hom it may concern:

Be it'known that we subject-ofthe King of Jsaxony, and HANS ASSIGN- 130 FABRIK VON HEYZPEN AKTIENGESELLSCHAFT, OF EBEUL,

mantimcronn or anomn'ric smrmc non 1W0 Drawing.) 7

CUR'r Pumice; a.

SCHMIDT a subject-of the King'of Prussia,

and resident the first of 6 Sedanstrasse, Rajdebeul, near Dresden, the second of 6 Gellertstrasse, Radebeul, near Dresden, -Kingdom of- Saxony, German Empire have invented a. newand useful Manufacturelof Aromatic QStibinic" Acid, of which the fol:

lowing is a specification-p It is a known fact thativery few aromatic stibinic acids have been hitherto-described Y t and the preparation of these acidswas very ghenylstibinic "derivatives were obtained;

- gigoii-the diazosgroup'by the usua meth follows:

- 49 1 6.7-per cent? of sodium hydroxid. This the nucleus diflicult,for thestartinglpoint was antimony stance on aromatlc compounds, diand triee, for instance -Bertchte d'.;Deutschen Ohemz'schen Gesellsckaft, a7 4621. 1 V l According to the process forming the ob ject of the present' 'mvention, aromatic stibinic acids of themonophenyl-series having are obtained very easily and in'a very bod, yield, bytreating aromatic diazo-compounds.

with salts of antimony 'trioxid and b split- The new process maybe performed as mixture 1s rapidly-cooled,whereupon apart of the sodiuinjsalt ofaantimonytnoxid sepanv rates in a" solid form. As soon as the temperature is about 0, iceis added. The mass is well stirred" and a solution'off-diazoben zenef rapidly added. .This solut on sfp'fre:

pa're'd' before-by adding .71 partso dium nitrite in the usual manner-.ito' a samtit er 93 part "of anilin dissolved 100.0.part

water and 1.47 arts of concentrated sulfuric? acid. e dine-solut on diluted acid. I It ma 4 "crystals, by crystallizmg from a hotmixture -one molecule of. -*aeiolecule ofania solution, filtering and; evaporating. "Salts which havebeen preparedwith molecule Specification of Letters Patent. Patented Man. 26, 191%. Application filed July it, 1912. Serial no. 709,779..

added to the antimony trioxid solution, a

strongdevelopment of nitrogen takes'place.

.After several hours the excess of sodium- The raw acid preparedthis way generallyv contains antimony trioxid from which it 1s separated in the following manner: 100 parts of-the acid are dissolved in 250 parts of hydrochloric acid of- 1.123 specific is filtered off and washed with gravity,adding a little animal charcoal and Y then saturating the hot solution with solid ammonium chlorid.- Phenylstibine oxychlo rid is formed which crystallizes in fine flakes and T is then washed-with a saturated solution of tered ofi after cooling. It

ammonium chlorid in hydrochloric acid. This oxychlorid ,is transformed into pure inexcess, filtering thesolution and preeip1- I .phenylstibinicacid b treating with a well-' tating pure phenylstibinic acid by adding a of alcohol and benzene.

mon salt or an: excess of sodium hydroxid be obtained )in-smalli .Phenylstibinicacid prepared according to 1 the present invention 1s easily soluble in so-' a the sodium. salt of phenylstibinic acid is Q precipitated- The sodium salt is slightly 1 soluble in water. *Solutions containing one half ofone er cent; of'this salt are quite stable at ordmary 'temperatureand of an en-.

tirel'y' neutral reaction;- If a solutionso formed is heated a. white precipitate is formed; which'jmayj-be'redissolved b addingsodiumhydroxid. Salts of an a solute'ly,

neutral-reaction are obtain y .d il i plliienylstibinic acid in i to ali hydroxid, .heatingthis w '100 alkalihydroxid have neutral reactiononly when they are highly diluted. Salts prepared with 1 or 2 molecules of an alkalihydroxid have an alkaline reaction whether they are diluted or not. x

6 Example ll.Pa1'aomyphen3 Zstibinic acid.

A representative of the most valuable class of aromatic'antimony compounds having the nucleus compound is poured into a solution of the sodium salt of antimony trioxid as described above. When the development of nitrogen I has ceased, the solution is saturated with carbon dioxi d in order to precipitate byproducts and a part of antlmony trioxid,

-".which has not reacted with the diaz'o comound. After filtering, themother liquid 1s treated with common salt, and para-0x v phenyl-stibinic acid is precipitated by ad ition of a diluted acid. It is slightly soluble in cold, and more readily soluble inhot water and easily soluble in diluted methylalcohol. When treated with ammonia water the acid is dissolved formin I solid ammonium salt is. recipitated, The acid is easily soluble in a alihydroxids and alkali-carbonates even if an Example Yllr -Para-acet Lamina-phenylf stz'bz'na'c a 1 150 parts; of mOnoacetyL- para-phenylendlamln 'are added toa iwell'cooled mixture Y of 147 parts of sulfuricfacid and 1000 parts the monophen yl serles having the nucleus 1 of water and diazotifzed'rby a solution of 11 parts of sodium nitrate. This mixture is added, to a' solution of antimony tri'oxid as described in Example 1. When the develop-; ment of nitrogen has ceased, the alkaline solutionis filtered, nearly neutralized by adding sulfuric acid and then saturated with carbonic dioxid, in order to-"precipitateany ing reacted: with the diazo solution. Tells mass is filtered a,. second. time and saturatedwith sodiumchlorid or othersodium salts,

I whereuponthe oainm salt of para-acetyl- $0 ,aIIIIIiCkPhBIlYl-Stlbllllti. acid precipitates.. It

' J separated from adherent inorganic salts yr 1 ppund employed. The new acids prepared diazotized mono acidyl para phenyle'ne- I v a saltyand' v85 when ammonium'hydrochlori is added, the

w geese of an, alkahhydroxld 1s added, but the alkali salts 40- are precipitated by common salt.

impurities and antimony tr oxid not hav sjsolving in inethy'lic alcohol. When 1 r "the'methyl alcohol is' evaporated at a lbw temperature, the sodium salt of-para-acetylamino-phenyl-stibinic acid isobtained. It 6'5;

is easilysoluble in ammonia water, alkaline h droxid s and carbonates, but diificultly soluble in an excess of an alkalihydroxid.. The process described in the foregoing ex- .amples may be carried out in a similar manner by employing other aromatic amino 'compounds in order to prepare the c 0rre-' spo'nding aromatic stibinic acids. The process may be modified in many respects accordingto the nature of the ammo comaccording to the present invention are ofgreat therapeutic and technical value.

What we claim is: I 1. The manufactureof aromatic antimony compgundslof the mono-phenyl-se'ries, consistingin treating an aromatic diazo-compound with antimony trioxid.

2. The manufacture of substitutiomprodnets of phenyl-stibinie acid, 'consistin in treating substitution'produ'cts of the iazo -benzol with antimony trioxid. I

3. The manufacture of para-acidyl-amino- 'phenyl-stibinic' acid, consisting in treating diamin with antimony trioxid. I

I 4. The manufacture of antimony oom-* pounds of the mono-.phenyl-series, consisting in treating aromatic diazocompounds with antimony trioxid, neutralizing and filtering the so obtained solution, 'preci itating the aromatic stibinic acid, dissol ing the crude acid in hydrochloric acid, saturating "the solutionwith easily soluble salts, removin by filtration the oxychlorid' 105 thereby derive ,treating-itrwith alkali carbonate and; transforming thesalt of the antimony compound'into free acid, by the 3 addition of a dilute acid;

5. The aromatic antimony compounds of i I xpon 1 water, alkali hydroxids and:oarbonates testimony that we claim the foregoing as our invention, we have signed our names 0f JllIlBalQlQ. VI -I I J .q-.-CURT PHILIPP. v SCHll/HD'llr- 1 Witnesses:

PAUL Aimee, {CLARE Smog, p

formingpowders easily soluble in ammonia 1n presence'of two witnesses thisi29th day/ 

